Institut des Sciences Analytiques UMR CNRS 5280, Université Claude Bernard Lyon1, Université de Lyon, 5 Rue La Doua, 69622 Villeurbanne, France.
Institut de Recherches sur la Catalyse et l'Environnement de Lyon, IRCELYON, UMR CNRS 5256, Université Claude Bernard Lyon1, Université de Lyon, 2 Av. Albert Einstein, 69626 Villeurbanne, France.
Int J Mol Sci. 2023 Jan 20;24(3):2123. doi: 10.3390/ijms24032123.
The cycloaddition of CO into epoxides to form cyclic carbonates is a highly sought-after reaction for its potential to both reduce and use CO, which is a greenhouse gas. In this paper, we present experimental and theoretical studies and a mechanistic approach for three catalytic systems. First, as Lewis base catalysts, imidazole and its derivatives, then as a Lewis acid catalyst, ZnI alone, and after that, the combined system of ZnI and imidazole. In the former, we aimed to discover the reasons for the varied reactivities of five Lewis base catalysts. Furthermore, we succeeded in reproducing the experimental results and trends using DFT. To add, we emphasized the importance of non-covalent interactions and their role in reactivity. In our case, the presence of a hydrogen bond was a key factor in decreasing the reactivity of some catalysts, thus leading to lower conversion rates. Finally, mechanistically understanding this 100% atom economy reaction can aid experimental chemists in designing better and more efficient catalytic systems.
环氧乙烷与 CO 的环加成反应是一种备受关注的反应，因为它有可能同时减少和利用温室气体 CO。本文通过实验和理论研究，对三种催化体系进行了机理研究。首先，我们以咪唑及其衍生物作为路易斯碱催化剂，然后以 ZnI 作为路易斯酸催化剂，之后是 ZnI 和咪唑的组合体系。在前一种情况下，我们旨在探索五种路易斯碱催化剂活性差异的原因。此外，我们成功地使用 DFT 重现了实验结果和趋势。此外，我们强调了非共价相互作用及其在反应性中的作用的重要性。在我们的案例中，氢键的存在是一些催化剂反应性降低的关键因素，从而导致转化率降低。最后，对这种 100%原子经济性反应的机理理解可以帮助实验化学家设计更好、更有效的催化体系。
